Pyridine → (S,E)-allyl 2-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrole-1-carbonyl)-4-methoxy-5-(triisopropylsilyloxy)phenylcarbamate

HRID 513359Notes

Reaction equation

HRID 513359 reaction equation
Cl[C:2]([O:4][CH2:5][CH:6]=[CH2:7])=[O:3].[NH2:8][C:9]1[CH:14]=[C:13]([O:15][Si:16]([CH:23]([CH3:25])[CH3:24])([CH:20]([CH3:22])[CH3:21])[CH:17]([CH3:19])[CH3:18])[C:12]([O:26][CH3:27])=[CH:11][C:10]=1[C:28]([N:30]1[CH:34]=[C:33](/[CH:35]=[CH:36]/[CH3:37])[CH2:32][C@H:31]1[CH2:38][O:39][Si:40]([C:43]([CH3:46])([CH3:45])[CH3:44])([CH3:42])[CH3:41])=[O:29].N1C=CC=CC=1>C(Cl)Cl>[Si:40]([O:39][CH2:38][C@@H:31]1[CH2:32][C:33](/[CH:35]=[CH:36]/[CH3:37])=[CH:34][N:30]1[C:28]([C:10]1[CH:11]=[C:12]([O:26][CH3:27])[C:13]([O:15][Si:16]([CH:17]([CH3:19])[CH3:18])([CH:23]([CH3:25])[CH3:24])[CH:20]([CH3:21])[CH3:22])=[CH:14][C:9]=1[NH:8][C:2](=[O:3])[O:4][CH2:5][CH:6]=[CH2:7])=[O:29])([C:43]([CH3:44])([CH3:46])[CH3:45])([CH3:41])[CH3:42]

Participants

5

Reactant 3

HCID 1049PyridineHCID 18052Allyl chloroformateHCID 86717762(S,E)-(2-amino-5-methoxy-4-(triisopropylsilyloxy)phenyl)(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrol-1-yl)methanone

Product 1

HCID 86717763(S,E)-allyl 2-(2-((tert-butyldimethylsilyloxy)methyl)-4-(prop-1-enyl)-2,3-dihydro-1H-pyrrole-1-carbonyl)-4-methoxy-5-(triisopropylsilyloxy)phenylcarbamateYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Allyl chloroformate (0.83 g, 6.88 mmol, 1.1 eq) was added to a solution of the amine 7 (3.6 g, 6.26 mmol, 1.0 eq) in dry DCM (80 mL) containing dry pyridine (1.09 g, 13.77 mmol, 2.2 eq) at −78° C. The dry ice was removed and the reaction mixture allowed to warm to room temperature. After stirring for a further 15 minutes, LC/MS indicated complete reaction. The organic phase was washed successively with 0.01N HCl (50 mL), saturated sodium bicarbonate (50 mL), brine (10 mL), dried over MgSO4, filtered and concentrated under reduced pressure to leave a pale yellow oil which was used in the next step without further purification (4.12 g, assumed 100% yield). LC/MS (4.862 min (ES+)), m/z: 659.2 [M+H]+.

Workup

  1. customThe dry ice was removed
  2. customreaction
  3. washThe organic phase was washed successively with 0.01N HCl (50 mL), saturated sodium bicarbonate (50 mL), brine (10 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customto leave a pale yellow oil which
  8. customwas used in the next step without further purification (4.12 g, assumed 100% yield)
  9. customLC/MS (4.862 min (ES+)), m/z

Sources & evidence

ORD record
ord-4b3e9c32ebca4a0c96cb8f86d67c190f
Source dataset
uspto-grants-2015_08
Patent number
US09102704B2

Reaction notes

Loading…